U.S. patent number 4,166,794 [Application Number 05/909,592] was granted by the patent office on 1979-09-04 for liquid bleach-softener compositions.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Seymour Grey.
United States Patent |
4,166,794 |
Grey |
September 4, 1979 |
Liquid bleach-softener compositions
Abstract
A liquid, bleach softener composition for use in one or more of
the wash, rinse and tumble dry cycles of a laundering process
comprising a water soluble peroxy bleaching agent, at least 50%
thereof being hydrogen peroxide, and a water soluble cationic
nitrogen softener compound, at least 50% thereof being an
aliphatic, quaternary ammonium compound and/or a cationic
heterocyclic imide such as an imidazolinium or pyridinium compound
in a weight ratio of softener to peroxy bleaching agent of about
5:7 to 5:1.
Inventors: |
Grey; Seymour (Somerset,
NJ) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
Family
ID: |
25427509 |
Appl.
No.: |
05/909,592 |
Filed: |
May 25, 1978 |
Current U.S.
Class: |
510/518; 510/308;
510/519; 510/525 |
Current CPC
Class: |
C11D
3/3947 (20130101); C11D 3/001 (20130101); C11D
3/0015 (20130101) |
Current International
Class: |
C11D
3/39 (20060101); C11D 3/00 (20060101); D06M
013/36 () |
Field of
Search: |
;252/8.8,8.6,95,102 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Schulz; William E.
Attorney, Agent or Firm: Blumenkopf; Norman Sylvester;
Herbert S. Grill; Murray M.
Claims
What is claimed is:
1. A liquid bleach, fabric-softener composition beneficially
adapted for use in one or more of the wash, rinse and tumble drying
cycles of a fabric-laundering process consisting essentially of, by
weight, from about 3 to 10% of water soluble peroxy bleaching
agent, at least about 50% thereof being hydrogen peroxide and from
about 3 to 25% of water soluble fabric softener compound, at least
about 50% thereof being cationic amine softener, the weight ratio
of softener to peroxy bleach being from about 5:7 to 5:1, the
balance of said composition being water or a mixture of water with
up to about 10% of water soluble lower alkanol.
2. A composition according to claim 1 wherein said bleaching agent
consists entirely of hydrogen peroxide.
3. A composition according to claim 2 wherein said softener
consists entirely of cationic amine softener agent.
4. A composition according to claim 3 wherein said softener is
cetyl pyridinium chloride.
5. A composition according to claim 3 wherein said softener is
hexadecyltrimethyl-ammonium bromide.
6. A composition according to claim 3 wherein said softener is
1-methyl-1-(tallowamidoethyl)-2-tallow imidazolinium chloride.
7. A composition according to claim 1 wherein said softener
comprises a cationic, heterocyclic imide.
8. A composition according to claim 1 wherein said softener is an
imidazolinium compound of the formula: ##STR3## wherein R.sub.1 is
alkyl of from 8 to 25 carbon atoms; R.sub.2 is alkyl of from 1 to 4
carbon atoms; R.sub.3 is hydrogen or alkyl containing from 8 to 22
carbon atoms; R.sub.4 is hydrogen or alkyl of from 1 to 4 carbon
and X is an anion.
9. A composition according to claim 1 wherein said softener is an
aliphatic quaternary ammonium compound of the formula: ##STR4##
wherein R.sub.5 is an aliphatic group of from 12 to 22 carbon
atoms; R.sub.6 is an aliphatic group of from 1 to 22 carbon atoms
and R.sub.7 and R.sub.8 are each alkyl groups of from 1 to 4 carbon
atoms.
10. A composition according to claim 1 wherein said softener is a
C.sub.12 -C.sub.22 alkyl pyridinium chloride.
11. A composition according to claim 1 having a pH of from about 4
to 5.
12. A composition according to claim 1 containing up to 50% of a
softener selected from the group consisting of 2 zwitterionic
quaternary ammonium compounds; nonionic tertiary phosphine oxides;
nonionic tertiary amine oxides; nonionic ethoxylated alcohol
compounds; ethoxylated alcohol sulfates; C.sub.8 -C.sub.20 alkyl
sulfate anionic synthetic detergents and ampholytic synthetic
detergents.
13. A composition according to claim 1 containing up to 50% of a
peroxy bleach compound selected from the group consisting of alkali
metal and ammonium perborates, percarbonate, monopersulfates and
monoperphosphates.
14. A composition according to claim 1 containing up to 10%
isopropanol.
15. A process for simultaneously bleaching and softening fabrics
being laundered comprising contacting said fabrics in one or more
of the wash, rinse and tumble drying cycles of the laundering
process with an effective bleaching and softening amount of the
composition of claim 1.
Description
FIELD OF THE INVENTION
The invention relates to bleach, fabric-softener compositions and
particularly to liquid bleach fabric softener compositions
beneficially adapted for use in one or more of the wash, rinse and
dryer cycles of an automatic laundry machine for imparting
simultaneously, significant bleaching, softening and detergency
effects to fabrics treated therewith.
BACKGROUND OF THE INVENTION
Description of the Prior Art
Conditioning compositions heretofore provided in the art for the
treatment of fabrics in one or more cycles of an automatic
laundering process usually include, with respect to bleaching and
softening in particular, either a specific type of bleaching agent
or softening agent. Combination of these materials in a unitary
composition is at best vaguely suggested as regards specific types
of ingredients, proportions and the like. Moreover, in such cases,
it is indicated as being necessary to use the bleach material in
solid form, and in substantial excess on a weight basis with
respect to any softener compound which might be peripherally
included within the relevant teaching. Peroxygen bleaches in such
cases are usually limited to the normally solid, water-soluble
types such as the alkali metal and ammonium perborates,
percarbonate, mono-persulfates and mono-perphosphates, species of
the foregoing including for example sodium and potassium perborates
and percarbonates. The aforementioned normally solid, inorganic
peroxygen bleaches are usually employed in combination with various
types of solid activators such as those disclosed in U.S. Pat. No.
3,130,165.
Dispensing of the solid bleach composition in the appropriate cycle
of the laundering process usually the dryer cycle, is often
effected by means of a solid carrier material including various
types of polymeric laminate and cellular structures, impregnated,
coated, or otherwise treated with the conditioning composition.
U.S. Pat. Nos. relevant to the foregoing discussion include
3,945,936; 3,870,145; 3,944,694; 3,956,556; 3,634,947; 3,947,971
and 3,283,357. For the most part, the foregoing patents relate to
the use of polyurethane-type carriers for the dispensing of either
bleach or softener compositions in a given cycle, mainly the dryer
cycle, of an automatic machine-laundering process.
The bleach component is usually added to the washing or drying
cycle in solid form as described in U.S. Pat. No. 3,945,936 and
British Patent Specification No. 1,456,592, the latter describing
the coating of bleach granules with fatty alcohol for bleach rate
and pH control in the washing medium. It is recognized that bleach
compositions in liquid form (wash cycle) are currently available
commercially; however, such compositions do not include, nor is
provision made for the inclusion of, softener.
Softener compounds, on the other hand, are conventionally added to
the laundering process suitably dispersed in a liquid carrier,
which may in turn be incorporated, e.g., by impregnation, into a
solid carrier support. Relevant in this regard are U.S. Pat. Nos.
3,442,692 and 3,632,396 describing the incorporation of liquid
solutions or dispersions of softener e.g., quaternary ammonium
compounds, into an absorbent sponge-type substrate and substrates
of open pore structure from non-woven cloth, paper, etc. of various
shapes such as puffs, balls and the like. Other U.S. Pat. Nos.
relevant to softener materials and structures for their dispensing
in a laundering process include 3,870,145; 3,944,694; 3,956,556;
3,634,947 and 3,947,971.
Conditioning compositions in liquid form offer several advantages
such as ready dissolution or dispersion in the washing media or on
damp fabrics in the laundry dryer; homogeneit via solubilization of
solid and/or liquid components in the conditioner solvent; facility
of dispensing e.g., by simple pouring; enhanced accuracy of
predetermined dosage amounts due to the increased volume of
conditioner solution being handled by the user, etc., By way of
contrast, the use of solid conditioning compositions entails
significant disadvantages such as the rather elaborate and
cumbersome structures required for their efficient dispensing in
the machine, as typified by the wide variety of carrier substrates
described in the prior are hereinbefore cited, as well as the
difficulties inherent in the compounding of solid ingredients in
the form of a coherent, homogeneous mass having adequate structural
as well as chemical stability.
In addition, conditioning compositions thus far provided are
capable of performing but a single function, e.g. bleaching or
softening, requiring, therefore, the use of separate compositions
during the washing-drying process according to a predetermined
sequence of addition. The inconvenience to the user readily is
apparent.
In accordance with the concept underlying the present invention, it
was found, surprisingly, that bleach and softener compounds,
subject to the requirements to be hereinafter discussed in detail,
could be effectively combined in a single liquid composition to
simultaneously provide effective bleaching, softening, detergency,
antistat properties, etc. when added to one or more of the wash,
rinse and dryer cycles of an automatic machine laundering process.
The result is somewhat surprising since it would normally be
expected that problems associated with, for example, compatibility
and stability of the involved ingredient and particularly in a
liquid environment normally considered to be highly conclusive to
undesired, fugitive side reactions, would militate against any
possible effectiveness. Thus, prior art attempts to combine
softener and bleach in a single composition have stressed the
requirement for solid rather than liquid vehicles and even then
under relatively stringent limitations as regards mutual
proportions of active ingredients, assuring for example, the
presence of bleach in at least substantial excess over softener.
Thus, the recognized tendency of many softeners to form insoluble
gels when present together with a peroxy bleaching agent in an
aqueous medium is a significant factor in the compounding of such
compositions.
Thus, a primary object of the present invention is to provide a
conditioning composition wherein the foregoing and related
disadvantages are eliminated or at least mitigated to a substantial
extent.
A further object of the invention is to provide a liquid, bleach
fabric-softener composition capable of simultaneously and
effectively bleaching and softening fabrics treatment
therewith.
A still further object of the invention is to provide such a
composition which may be added to one or more of the wash, rinse
and dryer cycles of an automatic machine washing and drying
operation.
Yet a still further object of the invention is to provide such a
composition having good stability on aging at ambient and elevated
temperatures over relatively prolonged periods of time.
Another object of the invention is to provide such a composition
having good compatibility of ingredients under varying conditions
of storage and use.
Still another object of the invention is to provide such a
composition completely safe for use with fabrics of dyed, synthetic
fibers such as Dacron, Dacron-cotton, permanent press as well as
natural fibers.
Yet another object of the invention is to provide a process
employing such composition in the conditioning of fabrics in a
laundering process.
Other objects and advantages of the invention will become apparent
hereinafter as the description proceeds.
DETAILED DESCRIPTION OF THE INVENTION
The attainment of the foregoing and related objects is made
possible in accordance with the invention which in its broader
aspects includes a liquid, bleach, fabric-softener composition
advantageously adapted for use in one or more of the wash, rinse
and tumble drying cycles of a laundering process consisting
essentially of, by weight, from about 3 to 10% of water-soluble
peroxy bleaching agent, at least about 50% thereof being hydrogen
peroxide, and from about 3 to 25% of water soluble or dispersible
fabric softener compound, at least about 50% thereof being cationic
amine softener, the weight ratio of softener to peroxy bleach being
from about 5:7 to 5:1, the balance of said composition being water
or solution thereof with up to 10% of lower alkanol.
In a further aspect, the invention includes a process of
conditioning fabrics by simultaneous bleaching and softening
thereof comprising contacting said fabrics in one or more of the
wash, rinse and tumble drying cycles of a laundering process with
an effective bleaching and softening amount of the composition
above described.
In accordance with the invention, at least about 50% and more
preferably, at least about 75% of the peroxy bleaching agent is
hydrogen peroxide. In the present invention, hydrogen peroxide is
somewhat unique and atypical within the broad class of known peroxy
bleaches, exhibiting a highly satisfactory level of stability when
exposed to varying conditions of temperature despite the presence
of the softener compound. Moreover, the bleaching activity of the
hydrogen peroxide and thus its ability to remove oxidizable stains
from treated fabrics is apparently wholly unaffected by the
softener compounds despite thier prolonged periods of standing at
elevated temperatures, e.g. up to about 130.degree.-140.degree. F.
The stable condition obtains despite the recognized activity of
hydrogen peroxide in aqueous media and especially in the presence
of compounds capable of undergoing oxidation. Hydrogen peroxide is
generally supplied commercially in the form of an aqueous solution,
such as the 50% solution available on the market as Albone 50% CG.
Other water soluble peroxygen bleaching agents useful herein in
combination with the hydrogen peroxide i.e., auxiliary bleaching
agents, include, without limitation, the inorganic peroxy compounds
such as the alkali metal and ammonium perborates, percarbonates,
monopersulfates and monoperphosphates in their various hydrated
forms. Specific examples are sodium and potassium perborates,
sodium and potassium percarbonates and the like. Other useful
materials include the water soluble organic peroxy acids and/or the
water soluble salts, e.g. alkali metal salts, thereof such as
described in U.S. Pat. No. 3,749,673; the mixtures of organic
peroxy acids and persulfate bleaches described in U.S. Pat. No.
3,773,673. Activators for one or more of the aforementioned
bleaching materials may also be used in known manner such as
described in U.S. Pat. Nos. 3,130,165 and 3,945,936.
As indicated, the amount of auxiliary bleaching agent is less than
about 50% and preferably less than about 25% of the total bleach
employed. It will further be understood that any such auxiliary
bleach or amounts thereof having an adverse effect upon the
composition in terms of stability, functionality, and the like are
excluded as to such amounts and types. In any event, in accordance
with the highly preferred embodiment of the invention, the bleach
component is solely hydrogen peroxide.
The concentration of peroxy bleach in the composition is from about
3 to 10% by weight with a range of 4 to 8% being preferred, the
value selected in a specific instance being such as to provide a
softener: bleach weight ratio in the final composition of from
about 5:7 to 5:1. Within the range given, the specific amount
selected mainly has reference to the severity of the laundering
problem contemplated for the product composition.
Softener compounds for use herein fall into the general category of
cationic amines, this term intended to cover cationic imides as
well. Thus, softeners of the aliphatic quaternary ammonium types as
well as cyclic imides are included such as the imidazolinium and
pyridinium salts. In general, the aliphatic quaternary ammonium
softeners can be represented according to the following structural
formula ##STR1## wherein R.sub.5 is an aliphatic, eg. alkyl, group
of from 12 to 22 carbon atoms; R.sub.6 is an aliphatic eg. alkyl,
group of from 1 to 22 carbon atoms and R.sub.7 and R.sub.8 are each
lower alkyl groups of 1 to 4 and preferably 1 to 3 carbon atoms,
and X is a water-soluble salt forming anion, such as a halide,
i.e., chloride, bromide, iodide; a sulfate, a citate, hydroxide,
methosulfate or similar inorganic or organic solubilizing mono-or
dibasic radical. Examples of quaternary ammonium softeners useful
herein include, without necessary limitation, hexadecyltrimethyl
ammonium bromide, this being a particularly preferred species;
hydrogenated ditallow dimethyl ammonium chloride; ethoxylated (n=3)
distearyl methyl ammonium chloride; dihexadecyl dimethyl ammonium
chloride; diotadecyl dimethyl ammonium chloride; dieicosyl
dimethylammonium chloride; didocosyl dimethyl ammonium chloride;
dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl
ammonium acetate; ditallow dimethyl ammonium nitrate; etc.
Another and preferred class of cationic nitrogen softener for use
herein are the imidazolinium salts which can be represented
according to the following structural formula: ##STR2## wherein
R.sub.1 is alkyl of from 8 to 25 carbon atoms; R.sub.2 is alkyl of
from 1 to 4 carbon atoms; R.sub.3 is hydrogen or alkyl containing
from 8 to 22 carbon atoms; R.sub.4 is hydrogen or alkyl of from 1
to 4 carbon atoms and X is an anion having the aforedefined
significance. Examples of compounds within the above formula are:
1-methyl-1-(tallowamidoethyl)-2-tallow imidazolinium methyl sulfate
this being a particularly preferred species and available
commercially as varisoft 475 softening agent and 2-heptadecyl-1,
1-methyl (2-stearoylamido) ethyl imidazolinium methyl sulfate.
Compounds particularly preferred herein are those within the above
formula wherein R.sub.1 and R.sub.3 are alkyls of from about 12 to
22 carbon atoms.
Another preferred class of softening agents for use herein are the
alkyl (C.sub.12 to C.sub.22) pyridinium chlorides and alkyl
(C.sub.12 to C.sub.22)-alkyl(C.sub.1 to C.sub.3)-morpholinium
chlorides. A particularly preferred species of this type of
softener is cetyl pyridinium chloride (monohydrate).
The softener compound above described may be employed singly or in
admixtures comprising tow or more thereof and in a total
concentration of from about 3 to about 25% by weight of product
composition. The value selected is such as to provide a softener:
peroxy bleach weight ratio of from about 5:7 to 5:1 as previously
indicated. The indicated amounts of softener and bleaching agent,
as regards total concentration in the product composition are such
as to provide effective softening and bleaching having reference to
the wide disparity in the severity of the cleaning problems
normally encountered with both synthetic type and natural
fabrics.
It will be understood that the foregoing formulae are used to
define preferred classes of softener and are not to be considered
as limitative. Thus, in accordance with preferred practice,
softeners comprising cationic nitrogen compounds of heterocycle
structure, i.e., the cationic imides are generally useful herein.
Those compounds within the formulae given are those generally found
to assure optimum results in accordance with the objectives of the
present invention.
The aforedescribed softeners constitute at least about 50% and
preferably at least about 75% of the total softener used. In
accordance with a highly preferred embodiment, such softeners
comprise the sole softener component. Auxiliary softeners useful
herein are well known in the art and may, in general, be selected
from a relatively wide variety of materials. Examples include,
without necessary limitation (a) the zwitterionic quaternary
ammonium compounds such as
3-(N-elcosyl-N,N-dimethyllammonio)-2-hydroxypropane-1-sulfonate;
3-(N-eicosyl-N.N-dimethylammonio) propane-1-sulfonate;
3-(N-docosyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate;
3-(N-tetracisyl-N,N-dimethylammonio)-propane-1-sulfonate;
3-(N-hexacosyl-N,N-dimethylammonio)2-hydroxypropane-1-sulfonate and
the like; (b) nonionic tertiary phosphine oxide such as
eicosyldimethylphosphine oxide; docosyldi(2-hydroxyethyl phosphine
oxide; hexacosyldimethylphosphine oxide; dicosyldiethylphosphine
oxide; eicosylmethylethylphosphine oxide; tricosyldiethylphosphine
oxide; pentacosyldimethylphosphine oxide;
heptacosyldimethylphosphine oxide and the like; (c) nonionic
tertiary amine oxides such as eicosyl-bis-(B-hydroxyethyl) amine
oxide; docosyldimethylamine oxide; tetracosyldimethylamine oxide;
2-hydroxyeicosyldiethylamine oxide; tricosyldimethylamine oxide;
tetracosyldiethylamine oxide and the like; (d) nonionic ethoxylated
alcohol compounds generally comprising the reaction product of
C.sub.20 -C.sub.30 alcohols with from 3 to 45 molestheylene oxide;
(e) ethoxylated alcohol sulfates comprising the sulfated
condensation products of C.sub.20 -C.sub.30 alcohols with 1-20
moles of ethylene oxide; (f) C.sub.8 -C.sub.20 alkyl sulfate
anionic synthetic detergents; (g) ampholytic synthetic detergents,
softeners of the aforedescribed types being more fully described,
for example, in U.S. Pat. No. 3,843,395. Again, softener materials
or amounts thereof which materially, adversely affect the stability
or functionality of the product composition are excluded herein as
to such types and/or amounts.
Softener materials particularly preferred for use herein comprise
the cationic nitrogen softeners of the heterocyclic imide type, the
preferred materials within this class being the imidazolinium and
pyridinium salts. It appears that these materials exhibit greater
stability on standing and particularly at elevated temperatures
when compared to softeners of the aliphatic quaternary ammonium
type. This is confirmed by experimental evidence gained from aging
tests conducted with representative species of each of the
preferred classes of aliphatic quaternary ammonium, imidazolinium
and pyridinium softeners.
Table I below summarizes the test results obtained upon aging,
under the conditions specified, the following composition in
accordance with the invention:
______________________________________ Ingredient % by weight
______________________________________ .sup.1 Hydrogen peroxide
12.0 (Albone 50% CG) Hexadecyltrimethyl 5.0 Ammonium bromide
Deionized water 83.0 100.0 ______________________________________
.sup.1 50% solution of hydrogenperoxide; H.sub.2 O.sub.2 = 6% of
composition pH adjusted with 25% H.sub.2 SO.sub.4 to 4.2
The aging test results are as follows:
TABLE I ______________________________________ (Initial HO
Concentration = 6.0%) % H O remaining after: (days) Temperature 30
60 ______________________________________ RT 6.0 5.4 100.degree. F.
3.8 2.4 120.degree. F. 3.7 2.4
______________________________________
The hexadecyltrimethyl ammonium bromide-H.sub.2 O.sub.2 system
exhibits reasonably good stability at room temperature; however,
relatively severe loss in the H.sub.2 O.sub.2 occurs at
temperatures of 100.degree. F. and 120.degree. F. as the data
indicates. Marked improvement in system stability is obtained when
a suitable H.sub.2 O.sub.2 stabilizer, such as
ethylenediaminetetraacetic acid (EDTA), is added to the
composition. In any event, for normal room temperature conditions
of storage, the stability of the system appears to be reasonably
adequate.
The following composition in accordance with the invention was
similarly tested:
______________________________________ Ingredient % by weight
______________________________________ Hydrogen peroxide 12.0
(Albone 50% CG) Cetyl pyridinium Chloride (monohydrate) 5.0
Deionized water 83.0 100.0
______________________________________
pH adjusted with 25% H.sub.2 SO.sub.4 to 4.5 with the following
result:
TABLE 2 ______________________________________ (initial H.sub.2
O.sub.2 concentration = 6.0%) % H.sub.2 O.sub.2 remaining after:
(days) Temperature 30 60 87 120
______________________________________ RT 6.0 5.9 5.9 5.9
100.degree. F. 5.9 5.7 5.7 5.7 120.degree. F. 5.8 5.7 5.7 5.7
______________________________________
Stability of the pyridinium chloride/H.sub.2 O.sub.2 system is
excellent at both room and elevated temperatures with about 95% of
the H.sub.2 O.sub.2 remaining after a period of about 4 months at
the relatively severe storage temperature of 120.degree. F.
The following composition in accordance with the invention was
similarly tested:
______________________________________ Ingredient % by weight
______________________________________ Hydrogen peroxide 12.0
(Albone 50% CG) .sup.1 Varisoft 475 6.7 Deionized water 81.3 100.0
______________________________________ pH adjusted to 4.5 with 25%
H.sub.2 SO.sub.4 .sup.1 1-methyl-1-(tallow amidoethyl)-2-tallow
imidazolinium methyl sulfate; 75% AI = 5.0% softener with the
following results:
TABLE 3 ______________________________________ (initial H.sub.2
O.sub.2 concentration = 6%) % H.sub.2 O.sub.2 remaining after:
(days) Temperature 45 75 120 195
______________________________________ RT 6.0 6.0 6.0 5.6
100.degree. F. 6.0 6.0 5.9 5.2 120.degree. F. 5.9 5.8 5.8 5.0
______________________________________
Stability of the imidazolinium salt/H.sub.2 O.sub.2 system is also
excellent at both room and elevated temperatures with about 97% of
the H.sub.2 O.sub.2 remaining after a period of about 4 months at
the high storage temperature of 120.degree. F. Not until a period
of about 61/2 months had elapsed at temperatures of 100.degree. and
120.degree. F. was there any appreciable loss of H.sub.2
O.sub.2.
Similar testing conducted with respect to the softener component
gave comparable results, i.e., appreciable loss of softener, e.g.
varisoft 475, did not occur until a period of 4 months had elapsed
and then only at a temperature of 120.degree. F. At a temperature
of 120.degree. F., about 90% of the softener remained after a
period of 105 days. Even better results obtained at temperatures
below 120.degree. F.
Similar results are obtained when the above tested softeners are
replaced wholly or in part by other of the primary softeners
included by Formulae A & B and the pyridinium compounds
hereinbefore given. Partial substitution of the primary softener
and H.sub.2 O.sub.2 with the auxiliary materials previously
described tends to diminish the stability of the composition and
particularly when such replacement is on the order of 50%. In such
cases, the use of stabilizers such as the EDTA previously mentioned
tends to promote stability.
Most desirably, the pH of the present liquid, bleach fabric
softener compositions should be maintained on the acid side e.g.,
from about 4 to 5, with a range of 4.3 to 4.7 being particularly
effective. The acid pH appears to assure not only good composition
stability but bleach and softener effectiveness as well. In
addition, more favorable effects as regards detergency and
antistatic properties obtain at the acid pH. The acid pH assumes
even greater importance in these regards as the concentration of
the peroxy and softener compounds in the composition is increased
within the limits hereinbefore given, i.e., H.sub.2 O.sub.2
concentration of up to about 10% and softener concentrations of up
to about 25%. The use of buffers and H.sub.2 SO.sub.4, NaO.sub.4
and the like is recommended should pH adjustment be necessary.
One of the truly surprising aspects of the present invention is
that the softener component when used as described, in no way
adversely affects the stain removal capacity of the peroxy
bleaching agent and particularly the hydrogen peroxide. Testing
indicates the bleach and softener compounds herein to be
satisfactorily compatible under normal and even abnormal conditions
of storage and use. When tested against commercial wash cycle
bleaching compositions containing hydrogen peroxide in identical
and greater amounts, the instant compositions are at least as
effective as regards the removal of oxidizable stains from a
variety of fabrics and particularly dyed fabrics of synthetic
fibers, permanent press. In terms of softening effects, the present
compositions are markedly superior. Moreover, these results obtain
when comparative testing is carried out in the dryer as well as
wash cycles of an automatic machine laundering operation. No fabric
discoloration or other untoward effect can be observed indicating
the present compositions to be completely safe with even the more
problematical types of fabrics.
Similarly, the instant, compositions compare at least favorably
when tested against commercial softener compositions on the basis
of identical softener concentration. Again, the favorable results
obtain when testing is carried out in the wash, rinse and dryer
cycles of the laundering process.
For optimum results, it is usually recommended that the softener
concentrations within the higher portion of the range hereinbefore
given be used should the instant composition be intended fpr use in
the dryer. For such application, it is advisable that the liquid
bleach fabric softener composition be relatively quickly dispensed
onto the damp fabrics, e.g., during the first 15 minutes of the
normal 60 minute dryer cycle to assure uniform and effective stain
removal. Higher softener concentration thus assures complete and
uniform contacting with the fabrics. However, it should be
understood that even at the lower softener concentration, the
instant compositions compare well with the commercial formulae as
the examples will make clear.
In some cases, slight gel formation may be observed in formulating
the instant compositions with the use of higher levels (on the
order of 25-50%) of auxiliary softener. This can be remedied for
the most part by the use of small amounts of thinning agent such as
NaCl, NaNO.sub.3 and the like.
The present compositions can be introduced to the appropriate
cycle(s) of the laundering process by a variety of means including
simple pouring, the use of a substrate impregnated with the
bleach-softener composition, a variety of container means provided
with a plurality of perforations for metered release of the
composition, e.g. perforated plastic bottle sich as polyethylene.
One embodiment found to be particularly effective is the use of
HANDIWIPE.TM. or other similar fabric substrate impregnated with an
effective bleaching and softening amount of the instant
composition. This embodiment is especially effective for use with
damp fabrics in the laundry dryer. Alternatively, an appropriate
amount of the bleach-softener composition can be added to a
suitable perforated container, the perforations being covered by an
adhesively bonded strip readily removable by the user at the time
of use. The container can be provided with an adhesive backing
enabling its ready attachment to the internal portion of the dryer,
e.g., dryer door, the stationary unit, or a suction cup device
appropriately positioned within the dryer. The substrate and
container methods for product dispensing are particularly effective
for product addition to the dryer. In any event, dispensing of
product should be completed as a general rule within the first 15
minutes of the dryer cycle.
The total amount of bleach fabric softener composition added to the
wash, rinse and or dryer cycles should in any event be effective to
accomplish the desired level of stain removal and softening. The
term "effective" amount as used herein is to be accorded its
conventional and art-recognized significance in connoting an amount
sufficient to soften and stain-clean the fabric being treated. It
is appreciated that the severity of the stain removal problem,
e.g., tea and wine stains, may necessitate the use of greater
"effective" amounts. The term "effective" is to be interpreted
having reference thereto. In any event for the vast majority of
laundering applications, sufficient of the bleach-softener
composition to provide a concentration in the wash medium of at
least about 100 to 150 ppm is generally effective. When added to
the dryer having a normal dryer load, sufficient of the bleach
softener composition to provide about 2.5 to 3 g of softener and
0.7 to 1.1 g of peroxy bleach is found to be more than adequately
effective. Thus, softener quantities as small as about 1.5 g per
normal dryer load are found to provide appreciable softening and do
not suffer significantly by comparison with currently available
commercial brands of softener specifying the use of such quantities
as to provide about 3 g of softener per normal dryer load.
The following examples are for purposes of illustration only and
are not to interpret as necessarily constituting a limitation on
the invention. All parts are by weight unless otherwise given.
Detergent where used has the following composition:
Detergent A
10% sodium linear tridecyl benzene sulfonate
2% C14-C15 fatty alcohol with an average of 11 ethylene oxide
groups
2% mixed sodium coconut/tallow fatty acid soap
35% pentasodium tripolyphosphate
7% sodium silicate (Na.sub.2 O:SiO ratio 1:2.35)
6.5% sodium carboxy methyl cellulose
balance sodium sulfate
Example 1 compares the stain removal and softening effects of a
composition in accordance with the invention with a commercial
bleach containing H.sub.2 O.sub.2 when each is added in separate
runs to the wash cycle of General Electric automatic washing
machine equipped with temperature control means and automatic wash,
rinse and spin dry cycles.
EXAMPLE 1
120 g (1/2 cup) of the following composition
______________________________________ Ingredient % g/H.sub.2
O.sub.2 g/varisoft ______________________________________ H.sub.2
O.sub.2 (50% Albone CG) 12.0 7.2 -- Varisoft 475 6.7 -- 6.0
Deionized water 81.3 -- -- 100.0
______________________________________
(a) is added by following to the laundry machine containing test
fabrics of Dacron-cotton (50:50), permanent press. About 11/4 cup
of detergent A is added therewith. Washing is conducted as
recommended by the manufacturer using tap water at 100.degree. F.
The test fabrics after completion of the wash rinse and spin dry
cycles are dried in a tumble dryer for 1 hour at the normal
setting.
(b) The above procedure is repeated but replacing the Varisoft
bleach-softener composition with 120 g (1/2 cup) of a commercial
wash cycle bleach containing 6% H.sub.2 O.sub.2, the balance water
to provide 7.2 g of H.sub.2 O.sub.2 in the wash water. The H.sub.2
O.sub.2 contents of the Varisoft and commercial bleach runs are
thus identical.
Reflectance readings taken on the test fabrics before and after
laundering (initial reflective readings being identical in each
case for the comparative test run) by standard techniques gives the
following results (.DELTA. Rd)
______________________________________ .DELTA. Rd Composition Tea
Grape Wine ______________________________________ (a) 1.9 30 31 (b)
2.3 31 31 ______________________________________
The stain removal capacity of the Varisoft composition (a) for the
same concentration of H.sub.2 O.sub.2 is essentially equal to
commercial bleach run (b). Softness ratings taken on the test
fabric by 5 independent panelists establish the Varisoft
composition to have markedly superior softness to the composition
of run (b).
EXAMPLE 2
Example 1 (a) and (b) is repeated except that the Varisoft
composition is inpregnated into a HANDIWIPE.TM. specimen and then
added to the washing machine. The bleaching and stain removal
results are essentially the same as those of Example 1.
EXAMPLES 3 & 4
Examples 1 and 2 are repeated except that the concentration of
Varisoft is increased to 16% to provide a softener bleach ratio of
about 14.4:7.2 or 2:1. The bleach and softener results are
essentially similar to those of Examples 1 and 2, the Varisoft
composition providing a yet greater measure of softness.
EXAMPLE 5
(a) Example 1(a) is repeated except that the Varisoft composition
in the amount of 60 g (1/4 cup) is added to the machine immediately
upon commencement of the rinse cycle to provide 3.6 g and 3.0 g of
H.sub.2 O.sub.2 and softener, respectively,
(b) part (a) is repeated except that the Varisoft composition is
replaced by an equivalent amount of a wash cycle commercial
softener composition containing the same amount of softener used in
part (a). In addition, 11/4 cup of detergent is added in this
run.
Stain removal and softness data are taken as in Example 1 with the
following results.
______________________________________ .DELTA. Rd Composition Tea
Grape Wine ______________________________________ (a) 1.2 32 31 (b)
1.3 27 27 ______________________________________
The Varisoft composition is markedly superior in terms of stain
removal; a measure of superiority might be expected since the
commercial softener does not contain bleach. However, the
commercial softener is augmented with detergent as indicated.
Nevertheless, stain removal is clearly inferior to the Varisoft
run. Even more striking is the fact that softness ratings taken on
the test samples by 5 independent panelists indicated the Varisoft
composition to be at least equal and in some cases superior to the
commercial softener product in terms of softeness.
EXAMPLE 6
Example 5 is repeated except that the Varisoft composition
impregnated into a HANDIWIPE.TM. specimen and then added to the
rinse cycle. The bleach and softening results are essentially
similar to those of Example 5.
EXAMPLE 7
Example 6 is repeated except that the Varisoft composition,
impregnated into a HANDIWIPE.TM. specimen in the amount of 30 g
(1/8 cup), is added to the damp test fabrics (normal dryer load) in
a laundry dryer to provide 1.8 g H.sub.2 O.sub.2 and 1.5 g
softener.
In a separate run (b) an equivalent amount of the commercial
softener composition (1.5 g) is added directly to the damp test
fabrics in the laundry along with 11/4 of detergent A. Drying is
carried out at the normal setting, in accordance with the
manufacturer's specifications, for 1 hour.
Stain removal and softness data are taken as previously described
with the following results.
______________________________________ .DELTA. Rd Composition Tea
Grape Wine ______________________________________ (a) 10 41 40 (b)
1.3 27 27 ______________________________________
Again, the difference is stain removal is pronounced in favor of
the Varisoft composition despite the use of significant amounts of
detergent in the commercial softener run, which would ordinarily be
expected to significantly boost the detergency and thus stain
removal ability of the commercial softener.
As indicated by the results of Examples 1-7, the instant
bleach-softener compositions are capable of providing at least
equal softness and stain removal in all cycles of the laundering
process when compared to separately provided commercial softener
and bleach compositions. These results obtain whether dispensing of
the instant product be by simple pouring (as is necessarily the
case with the commercial compositions) or by means of an
impregnated substrate as typified by the HANDIWIPE.TM. article.
When the various procedures of Example 1-7 are repeated but
replacing the Varisoft 475 with equivalent amount of (a)
hexadecyltrimethyl ammonium bromide and (b) cetyl pyridinium
chloride (monohydrate), essentially the same results are obtained
i.e., oxidizable stain removal and softness results compare at
least equally with the commercial compositions separately provided
for such purposes. In most cases, the cetyl pyridinium chloride
compositions, representatives of the cationic cyclic imides for use
herein, are superior to the hexadecyltrimethyl ammonium bromide,
the latter representative of the aliphatic, cationic quats herein
described, with respect to both stain removal and softness.
However, the aliphatic softener in any event compares favorably
with the commercial bleach and softener compositions in softness
and stain removal results.
EXAMPLE 8
The procedure of Example 1 is repeated but using a wash temperature
of 120.degree. F. The test fabrics in each case comprise
Dacron-cotton (50:50) permanent press stained with grape juice,
bluberry pie filling and tea respectively. The compositions tested
are as follows:
(a) Varisoft composition of Example 1
(b) Commercial bleach composition containing 6% of H.sub.2 O.sub.2
(7.2 g)
(c) Detergent A above (0.15% in wash medium)
Reflective softness ratings are taken on the laundered fabric
samples as described
______________________________________ Rd Blueberry Pie Composition
Tea Grape Filling ______________________________________ (a) 13.0
63.6 67.2 (b) 8.5 62.9 65.0 (c) 4.9 62.6 62.4
______________________________________
Each of the Varisoft and commercial bleach compositions (a) and (b)
is superior to the use of detergent alone (c). More striking here
is the marked superiority of the Varisoft composition over the
commercial formula in all categories and particularly with respect
to tea stain. In Example 1 wherein washing is carried out at
100.degree. F., composition (b) is slightly superior regarding tea
stain with essential parity obtaining for grape and wine stain. The
overall superiority of the instant compositions appears to become
increasingly manifest at the higher washing temperature and
particularly as regards normally difficult tea stain.
In the present example, the Varisoft composition (a) is definitely
superior to the commercial bleach (b) and detergent (c)
compositions as to softness, this being concluded by an independent
panel of testers. Composition (a) is likewise essentially equal to
a commercial wash cycle softener added in a separate run to the
wash cycle and having the same amount of softener as in composition
(a).
EXAMPLES 9 & 10
Example 8 is repeated but wholly replacing the Varisoft with (a)
hexamethyltrimethyl ammonium bromide and (b) cetyl pyridinium
chloride respectively. The softness and stain removal results are
essentially similar to those of Example 8, superiority over the
commercial bleach and detergent formula being conclusively
indicated from the data. Again, the cetyl pyridinium chloride
composition is superior to the hexadecyltrimethylammonium bromide
in both stain removal and softness.
EXAMPLE 11
Example 8 is repeated except that each of the Varisoft, commercial
bleach and commercial softener composition is added by pouring on
to the damp test fabrics in the laundry dryer. The test run using
detergent alone is omitted. Drying is carried out in a machine
dryer for about 1 hour at 160.degree.-170.degree. F.
Reflectance and softness ratings are taken as previously described
with the following results:
______________________________________ .DELTA. Rd Composition Tea
Grape Blueberry Pie ______________________________________ (a) 18.8
66.7 69.6 (b) 18.4 66.2 69.3 .sup.1 (c) 6.4 61.6 61.2
______________________________________ .sup.1 commercial softener
composition having same amount of softener as in (a) = 6.0g.
The Varisoft composition is slightly superior to the commercial
bleach run in all aspects tested, each of these compositions being
markedly superior to commercial softener (c). In terms of softness,
(a) is about equal to (c) each of which is noticeably superior to
(b).
EXAMPLES 12 & 13
Example 11 is repeated but wholly replacing the Varisoft with (a)
hexadecyl trimethyl ammonium bromide and (b) cetyl pyridinium
chloride. Similar stain removal and softness results are obtained.
Again, the cetyl pyridinium chloride is somewhat superior to the
hexadecyltrimethyl ammonium bromide in stain removal and softness
results.
EXAMPLE 14
The procedure of Example 11 is repeated. In this case however, the
compositions tested are as follows:
(a) 30 g of the Varisoft composition of Example 1 to provide 1.8 g
H.sub.2 O.sub.2 and 1.5 g softener with the damp test fabrics in
the laundry dryer.
(b) commercial softener to provide 3.0 g softener with the damp
test fabrics in the laundry dryer.
Reflective and softness readings are taken as previously described
with the following results:
______________________________________ .DELTA.Rd Composition Tea
Grape Wine ______________________________________ (a) 12 46 34 (b)
2.7 40 27 ______________________________________
Superior stain removal is clearly evident for the Varisoft
composition. The overall stain removal effectiveness of the
Varisoft composition is made more manifest by reference to the fact
that the amount of bleach (H.sub.2 O.sub.2) used is but one-quarter
(1.8 vs. 7.2 g) that of Example 11. In terms of softness, the
commercial composition (b) is slightly superior; however, the
margin of superiority is much less than what would be expected in
view of the fact that only 1.5 g Varisoft are used as compared to
3.0 g softener from the commercial product (b).
EXAMPLE 15
Example 14 is repeated except that the amount of Varisoft
composition (a) used in increased to 60 g thereby providing 3.6 g
H.sub.2 O.sub.2 and 3.0 g softener with the damp test fabrics in
the laundry dryer. Run (b) is identical with run (b) of Example
14.
Reflectance and softness readings are taken as described with the
following results:
______________________________________ Rd Composition Tea Grape
Wine ______________________________________ (a) 14 46 34 (b) 2.7 40
27 ______________________________________
Stain removal is about the same as for Example 14 with a
significant increase in tea stain removal for (a) being a notable
exception. In this example, the softness of test fabrics treated
with the Varisoft composition is at least equal to that of the
commercial softener (b), each of these compositions containing 3.0
g softener.
Similar results are obtained when the Varisoft in the preceding
examples is wholly replaced in equivalent amounts with (a)
hexadecyltrimethylammonium bromide and (b) cetyl pyridinium
chloride, the latter proving somewhat superior to the former. in
both stain removal and softness.
EXAMPLE 16
The procedure of Examples 14 and 15 is repeated with respect to the
following compositions.
(a) same as (a) in Example 14=1.8 g H.sub.2 O.sub.2 & 1.5 g
softener
(b) same as (a) in Example 15=3.6 g H.sub.2 O.sub.2 & 3.0 g
softener
(c) 70 g of (a) in Example 15=4.2 g H.sub.2 O.sub.2 & 3.5 g
softener
(d) 30 g of the following composition:
______________________________________ Ingredient % g/H.sub.2
O.sub.2 g/Varisoft ______________________________________ Deionized
water 74.7 -- -- Varisoft 475 13.3 -- 10 H.sub.2 O.sub.2 (Albone
50% CG) 12.0 6.0 -- 100.0
______________________________________
to provide 1.8 g H.sub.2 O.sub.2 and 3.0 g softener.
(e) commercial wash cycle bleach composition 120 g added to the
wash cycle with about 11/4 cup of detergent A to provide 7.2 g
H.sub.2 O.sub.2.
Reflectance readings taken on the test fabrics in the manner
described yield the following results:
______________________________________ Rd Composition Tea Grape
Wine ______________________________________ (a) 12 46 34 (b) 14 46
34 (c) 14 46 34 (d) 12 45 34 (e) 5 37 30
______________________________________
Use of the instant bleach softener compositions in the laundry
dryer is in all aspects significantly superior to the use of the
commercial bleach composition (e) in the wash cycle in the manner
prescribed by the manufacturer. The vast improvement is obtained
despite the use of significantly less H.sub.2 O.sub.2 in the
instant composition as compared to the commercial bleach. Thus,
compositions (a) and (d) which contain but one-quarter the amount
of the H.sub.2 O.sub.2 of commercial bleach (e) nevertheless
provide markedly superior stain removal and particularly with
respect to tea stain. Runs (b), (c) and (d) are at least equal in
softness to a test run using 3.0 g commercial softener in the
dryer; run (a) is but slightly inferior to the commercial softener
run as to softness despite the use of but one-half the softener
amount.
EXAMPLE 17
Example 16 is repeated except that compositions (a),(b), (c) and
(d) are dispensed in the clothes dryer by means of a polyethylene
bottle container provided with a plurality of perforations for
release of bleach-softener composition. The perforations are sealed
by means of an externally applied sealing strip of masking tape
adhesively and removably bonded to the bottle. The sealing strip is
peeled off at the time the drying cycle is begun. The bottle is
secured to the inner stationary vent of the dryer by a bonding
adhesive provided on the container enabling ready removal and
refilling of the container upon completion of the drying cycle. The
container is designed such that the entire charge of
bleach-softener composition is dispensed onto the fabrics during
the initial 15 minutes of the drying cycle.
The stain removal and softness results are essentially similar to
those of Example 16.
The instant bleach softener compositions compare quite well with
the more conventional chlorine type cleaches in terms of oxidizable
stain removal. In terms of safety to colored synthetic fabrics, the
present compositions are quite superior.
EXAMPLE 18
The procedure of Example 1 is repeated except that the H.sub.2
O.sub.2 bleach of run (b) is wholly replaced with an equivalent
amount of a commercial chlorine bleach. Reflectance measurements
are taken as described with the following results:
______________________________________ Rd Composition Tea Grape
Wine ______________________________________ (a) 3.6 33 31 (b) 6 34
34 ______________________________________
The instant compositions as typified by the Vasisoft composition
itemized in Example 1, compare quite well with the commercial
chlorine bleach and particularly with respect to grape and wine
stain. Comparative runs testing the commercial (a) H.sub.2 O.sub.2
bleach and (b) softener composition against the chlorine bleach of
Example 18 indicated the instant compositions to be superior to the
commercial formulae.
As indicated in the foregoing examples, the improvements made
possible by the present invention are particularly manifest when
the bleach, fabric softener composition is added to the dryer over
a wide concentration range. Optimum results as to the dryer-added
embodiment obtain, however, when the amount of softener in the
composition is increased so as to provide a softener bleach ratio
of up to about 5:1. A particularly effective composition for such
use had the following composition:
______________________________________ % g/H.sub.2 O.sub.2
g/Varisoft 475 ______________________________________ H.sub.2
O.sub.2 (Albone 50% CG) 12 6 -- Varisoft 475 27 -- 20 Deionized
water 61 -- -- 100 ______________________________________
the ratio of softener to H O being about 3.3. Above a softener
bleach ratio of about 5, correlative increase in softening for
increased softener concentration appears to be negligible. In
contrast, it is found that excess of peroxy bleach above about 40%
with respect to softener leads to destabilizing effects adversely
affecting the softening and stain removal capabilities of the
bleach-softener composition.
The bleach and softener components herein defined can be
solubilized with water, preferably deionized, to reduce the
possibility of contamination and degradation effects caused by
impurities, or a mixture of water with up to about 10% of water
soluble, lower C.sub.1 -C.sub.4 alkanol such as propanol and/or
isopropanol, the latter being preferred. The use of alcoholic
solvents is especially preferred when using softener concentrations
within the higher portion of the range given.
As indicated previously, in accordance with a particularly
preferred embodiment of the invention, the softener component
comprises a cationic, heterocyclic imide such as typified by the
illustrated Varisoft. Accordingly, it is particularly preferred
that at least about 50% and preferably 75% of the softener
component be the cationic cyclic imide material.
Although the examples have been illustrated with respect to certain
preferred embodiments of the invention, it will be understood that
the invention is not limited thereto. Thus, similar results are
obtained when the exemplified cetyl pyredinium chloride,
hexadecyltrimethyl ammonium bromide and
1-methyl-1-(tallowamido-ethyl)-2-tallow imidazolinium methyl
sulfate are replaced with one or more of the cationic amine
softener compounds given hereinbefore and within the concentration
limits defined. However, as previously stated, non-cationic amine
softener, i.e. auxiliary softener, is to be used as a partial
replacement only within the limitations previously expressed.
* * * * *